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Para-Hydroxybenzoyl-Orthobenzoic  Acid  and 
Some  of  Its  Derivatives 

By  W.  R.  ORNDORFF  and  LOUISE  KELLEY 


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This  is  a  reprint  of  an  article  based  upon  a  thesis  submitted  to 
the  Faculty  of  the  Graduate  School  of  Cornell  University  for  the 
degree  of  Doctor  of  Philosophy  by  Louise  Kelley. 


Para-Hydroxybenzoyl-Orthobenzoic  Acid  and 
Some  of  Its  Derivatives 

By  W.  R.  ORNDORFF  and  LOUISE  KELLEY 


This  is  a  reprint  of  an  article  based  upon  a  thesis  submitted  to 
the  Faculty  of  the  Graduate  School  of  Cornell  University  for  the 
degree  of  Doctor  of  Philosophy  by  Louise  Kelley. 


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»  •*« »  »»« *    *  •; 
.***»*.  »^»     , 


This  report  contains  in  condensed  form  all  the  experimental 
work  of  the  thesis  upon  which  it  is  based.  The  typewritten  copy 
of  the  thesis  is  on  file  in  the  Library  of  Cornell  University. 


\ 


[Reprinted   from    the    Journal   of   The    American    Chemical   Society, 
Vol.  5.     No.  7.     July,  1922.] 

[CONTRIBUTION    FROM.  THE    CHEMICAL    LABORATORY    OF    CORNER    UNIVERSITY] 

PARA-HYDROXYBENZOYL-ORTHO-BENZOIC  ACID   AND   SOME 
OF  ITS  DERIVATIVES 

BY  W.  R.  ORNDORFF  AND  LOUISE  KELLEY 

Received  November  21,  1921 

p-Hydroxybenzoyl-0-benzoic  acid  was  first  made  by  Friedlander,1 
who  prepared  it  by  the  decomposition  of  phenolphthalein-oxime  with  dil. 
sulfuric  acid.  In  1917  Orndorff  and  Murray2  prepared  the  acid  from  phe- 
nolphthalein  by  this  method  and  studied  its  condensation  with  various 
phenols.  They  also  prepared  a  diacetate  of  the  acid,  melting  at  137-140  °. 

This  investigation  was  undertaken  for  the  purpose  of  studying  the 
properties  and  characteristic  reactions  of  /?-hydroxybenzoyl-o-benzoic 
acid  and  of  some  of  its  derivatives. 

Experimental 

The  melting  points  given  in  the  following  pages  are  uncorrected  and  were 
made  in  an  electrically  heated  Dennis  melting-point  apparatus,3  the 
heat  being  so  regulated  as  to  give  a  rise  in  temperature  of  1  °  in  5  seconds. 
The  thermometer  used  was  a  standard  one..  An  electrically  heated 
tube4  was  used  for  bringing  substances  to  constant  weight  by  means  of 
heat.  Samples  for  analysis  were  dried  in  a  desiccator  over  cone,  sulfuric 
acid.  The  values  used  for  the  atomic  weights  are  those  given  in  the  1920 
table  of  international  atomic  weights.6  In  stating  the  approximate 
solubility  in  various  solvents  of  the  substances  obtained  the  classification 
of  Mulliken6  was  used. 

£-Hydroxybenzoyl-0-benzoic  Acid. — This  substance  was  prepared 
from  phenolphthalein  by  the  method  of  Friedlander.  The  yield  of  crude 
acid  from  100  g.  of  phenolphthalein  is  75. 0  g.  (calculated  76. 05  g.).  The 
crude  acid  has  a  light  greenish-yellow  color,  which  is  easily  removed  by 
one  recrystallization  from  hot  water,  provided  the  solution  is  boiled  with 
bone  black.  The  acid  crystallizes  from  hot  water  as  colorless  plates  which 
are  usually  diamond-shaped  with  irregular  edges.  It  is  very  soluble  in 
hot  95%  alcohol,  hot  methyl  alcohol  and  hot  glacial  acetic  acid,  diffi- 
cultly soluble  in  hot  water,  very  difficultly  soluble  in  hot  benzene,  soluble 
in  cold  aqueous  5%  sodium  hydroxide  giving  a  pale  yellow  solution,  and 
is  soluble  in  cold  cone,  sulfuric  acid,  giving  a  bright  yellow  solution,  from 
which  £-hydroxybenzoyl-o-benzoic  acid  may  be  recovered  unchanged. 
The  pure  acid  melts  at  213°  with  evolution  of  gas. 

Friedlander,  Ber.,  26,  176  (1893). 

Orndorff  and  Murray,  THIS  JOURNAL,  39,  679  (1917). 

Dennis,  /.  Ind.  Eng.  Chem.,  12,  366  (1920). 

Am.  Chem.  >.,  48,  477  (1912). 

THIS  JOURNAL,  41,  1886  (1919). 

Mulliken,  "Identification  of  Pure  Organic  Compounds,"  1905,  vol.  I,  p.  38. 


DERIVATIVES  OF  HYDROXYBENZOYL-BENZOIC  ACID  1519 

Some  of  the  pure,  desiccator-dried  acid  was  used  for  the  following  analy- 


ses. 


The  molecular  weight  of  the  acid  was  determined  by  titration  with 
0  1  N  sodium  hydroxide  solution,  using  methyl  red  as  indicator. 

Subs  (I)  0.2016,  (II)  0.1957,  (III)  .0.5008,  cc.  0.1  N  NaOH,  (I)  8.33,  (II)  8.08, 
(III)  20.68.  Calc.  for  C14H10O4:  242.15.  Found:  (I)  242.02,  (II)  242.20,  (III)  242.17. 
These  results  show  that  the  acid  titrates  as  a  monobasic  acid.  The  com- 
bustion analyses  gave  the  following  results. 

Subs  ,  0.1999,  0.1989;  CO2,  0.5093,  0.5048,  H2O,  0.0762,  0.0754.  Calc.  for  Ci4H10O4: 
C,  69.41;  H,  4.16.  Found:  C,  69.51,  69.24;  H,  4.27,  4.24. 

'The  solubility  of  the  acid  in  distilled  water,  95%  ethyl  alcohol,  methyl 
alcohol  and  benzene  at  21°  was  determined. 

Pts.  of  solvent         G.  of  acid  soluble 

which  dissolve  in  100  cc. 

golvent                                  1  part  of  acid  of  solvent 

Water                      1578.8  0.0632 

95%alcohol 36.00 

Methyl  alcohol 

Benzene 7193.2  0.0121 

£-Hydroxybenzoyl-o-benzoic  acid  is  a  7-ketonic  acid  and  in  the  free  con- 
dition probably  has  the  lactone  structure  I.  In  its  salts  and  esters 
has  the  ketone  structure  II. 

HOC6H4C(OH)C6H4  HOC6H4COC6H4COOM 

O C  =  0 

I  II 

A  similar  structure  has  already  been  suggested  for  2,4-dihydroxybenzoyl- 
o-benzoic  acid  by  Graebe,  Kohn  and  Huguenin7  and  for  benzoyl-0-ben- 
zoic  acid  by  Haller  and  Guyot,8  while  Graebe  .has  assumed  the  lactone 
structure  for  the  acetate  of  benzoylbenzoic  acid.9 

Action  of  Dry  Ammonia  Gas  on  £-Hydroxybenzoyl-o-benzoic  Acid.— When  dry 
ammonia  gas  is  passed  over  dry  £-hydroxybenzoyl-0-benzoic  acid  it  is  absorbed  an 
material  assumes  a  pale  yellow  color. 

Analyses     Subs.,  0.2375,   0.1335,   0.8153:    wt.   of  salt,  0.2788,  0.1569,  0.9588. 
Calc.  for  C14H1004.(NH3)2.5:  NH3,  14.95.     Found:   14.81,  14.91,  14.97. 

The  acid  exhibits  toward  ammonia  an  abnormal  absorptive  power,  since  it  takes 
up  2  5  molecules  of  ammonia.     On  standing  in  an  evacuated  desiccator  over  cone,  sul- 
furic  acid  the  material  loses  ammonia  slowly  and  comes  to  constant  weight  whe 
one  molecule  of  ammonia  remains. 

Analyses.    Subs.,  0.1335,  0.8153 :  wt.  of  salt,  0.1430,  0.8735.      Calc.  for  C14H10O4.- 
(NH8):  NH3,  6.57.     Found:  6.64,6.66. 

'  Graebe,  Kohn  and  Huguenin,  Arch.  sci.  phys.  nat.,  30,  91  (1893). 

8  Haller  and  Guyot,  Compt.  rend.,  119,  140;  and  Btr.,  27,  Ref.,  664  (1894).    Bull, 
soc.  chim.,  [3]  25,  52  (1901). 

9  Graebe,  Ber.,  33,  2027  (1900). 


1520  W.  R.  ORNDORFF  AND  LOUISE 

This  mono-ammonium  salt  is  colored  only  slightly  yellow.  When  dry  air  was 
passed  over  it  at  80°  for  5  hours  it  suffered  no  loss  in  weight. 

/>-Hydroxybenzoyl-o-benzoic  acid  at  first  forms  with  dry  ammonia  an  unstable, 
slightly  colored,  ^'-ammonium  salt,  which  by  the  loss  of  ammonia  forms  the  stable 
mono-ammonium  salt.  It  is  probable  that  the  excess  of  ammonia  over  the  two  mole- 
cules is  attached  to  the  carbonyl  group. 

HOC6H4C(OH)C6H4  +  2NH3  >   NH4OC6H4COC6H4COONH4  > 

Unstable 

O C  =  0  HOC6H4COC6H4COONH4  +  NH, 

Stable 

Monosodium  Salt.— A  warm  solution  of  5  g.  of  £-hydroxybenzoyl-o-benzoic  acid 
in  25  cc.  of  absolute  ethyl  alcohol  was  added  to  a  solution  of  0.5  g.  of  sodium  (calculated 
for  monosodium  salt,  0.475  g.)  in  30  cc.  of  absolute  alcohol.  The  sodium  salt  began  to 
separate  almost  immediately  in  the  form  of  small,  colorless  needles.  These  were  filtered 
from  the  mother  liquor  and  washed  with  cold  absolute  alcohol.  The  salt  is  very  soluble 
in  hot  water  and  in  hot  95%  alcohol,  and  difficultly  soluble  in  hot  absolute  alcohol. 
It  turns  yellow  when  heated  to  110-120°,  and  the  anhydrous  salt  takes  up  water  in  the 
air  soon  becoming  colorless  again.  The  air-dried  salt  when  dried  hi  a  desiccator  lost 
only  2%  in  weight,  this  loss  being  due  to  alcohol  held  mechanically,  and  there  was  no 
change  in  color.  The  desiccator-dried  sample  was  analyzed  for  sodium  by  fuming 
down  with  cone,  sulfuric  acid. 

Analyses.  $ubs.,  0.3494,  0.4001:  Na2SO4,  0.0797,  0.0915.  Calc.  for  C14H9O4Na: 
Na,  8.70.  Calc.  for  C14H9O4Na,  C2H6OH:  Na,  7.41.  Found:  7.38,  7.41. 

The  molecule  of  alcohol  is  removed  by  heating  the  salt  in  a  current  of  dry  air  at 
130°. 

Analyses.  Subs.,  0.2360,  0.5523:  loss,  C2H6OH  at  130°,  0.0350,  0.0824.  Calc. 
for  Ci4H9O4Na,  C2H6OH:  C2H6OH,  14.85.  Found:  14.83,  14.92. 

Silver  Salt. — This  salt  was  prepared  by  heating  a  solution  of  £-hydroxybenzoyl- 
0-benzoic  acid  in  alcohol  with  a  solution  of  silver  nitrate  in  alcohol  and  water  for  2  hours. 
The  salt  separated  from  the  solution  on  cooling  as  small,  grayish  colored  crystals, 
slightly  soluble  in  cold,  more  soluble  in  hot  water.  The  salt  cannot  be  recrystallized 
from  hot  water  because  of  the  separation  of  metallic  silver.  It  is  slightly  soluble  in  hot 
or  cold  95%  alcohol,  and  the  solutions  soon  acquire  a  brownish  tinge. 

The  desiccator-dried  salt  was  analyzed  by  igniting  a  weighed  amount  in  a  porcelain 
crucible  and  weighing  the  metallic  silver  so  obtained. 

Analyses.  Subs.,  0.4014,  0.4008:  Ag,  0.1240,  0.1239.  Calc.  for  C14H9O4Ag- 
Ag,  30.91.  Found:  30.89,  30.91. 

The  molecular  weight  of  £-hydroxybenzoyl-o-benzoic  acid  calculated  from  these 
results  is  242.25  and  thus  confirms  the  results  of  the  titration  of  the  acid  with  0.1  N 
sodium  hydroxide  solution  (p.  1519). 

Barium  Salt.— This  salt  was  prepared  by 'heating  an  aqueous  solution  of  the  acid 
with  barium  carbonate  for  3  hours.  The  liquid  was  filtered  and  from  the  filtrate  there 
separated  on  standing  large,  6-sided,  greenish-yellow  crystals.  The  salt  is  difficultly 
soluble  in  hot  water  and  very  difficultly  soluble  in  hot  95%  alcohol.  The  pure  barium 
salt  softens  at  245°  and  melts  with  evolution  of  gas  at  259°. 

Dried  in  a  desiccator  the  salt  lost  only  0.17%  in  weight.  The  water  of  crystalliza- 
tion in  the  desiccator-dried  salt  was  determined  by  heating  portions  of  it  in  a  current  of 
dry  air  at  125°. 

Analyses.  Subs.,  0.5345,  0.5759:  loss  at  125°,  0.0294  00322  Calc  for 
C28H1808Ba.2H20:  H2O,  5.50.  Found:  5.50,  5.59. 


DERIVATIVES  OF  HYDROXYBKNZOYIv-BENZOIC  ACID  1521 

The  anhydrous  salt  was  then  analyzed  for  barium. 

Analyses.  Subs.,  0.5051,  0.5437:  BaSO4,  0.1885,  0.2031.  Calc.  for  C28H18O8Ba: 
Ba,  22.17.  Found:  21.96,  21.98. 

The  barium  salt  was  examined  by  Professor  A.  C.  Gill  of  the  Mineralogical  Depart- 
ment of  Cornell  University,  who  reported :  "This  salt  is  probably  triclinic.  Measure- 
ments gave  a  double  refraction  of  0.071." 

The  formula  of  the  barium  salt  is  HOC6H4COC6H4COOBaOOCC6H4COC6H4OH. 

Calcium  Salt. — The  calcium  salt  prepared  from  £-hydroxybenzoyl-o-benzoic 
acid  and  calcium  carbonate,  crystallizes  in  clusters  of  small,  pale  yellow,  glistening 
needles.  It  is  easily  soluble  in  hot  water  and  hot  95%  alcohol.  When  heated,  it 
softens  at  252°  and  melts  with  evolution  of  gas  at  262-263°. 

Heated  in  a  current  of  dry  air  at  125  °  for  a  few  hours,  the  air-dried  salt  loses  weight 
corresponding  to  2  molecules  of  water  of  crystallization.  Water  was  seen  to  condense  on 
the  sides  of  the  drying  tube. 

Analyses.  Subs.,  0.2793,  0.3051;  loss  at  125°,  0.0182,  0.0200.  Calc.  for  C28H18- 
O8Ca.2H2O:  H2O,  6.45.  Found:  6.52,  6.56. 

The  colorless  anhydrous  salt  was  analyzed  for  calcium. 

Analyses.  Subs.,  0.2611,  0.2851:  cc.  0.1  N  KMnO4,  9.96,  10.82.  Calc.  for  C28Hi8- 
08Ca:  Ca,  7.67.  Found:  7.64,  7.60. 

The  air-dried  salt  was  analyzed  in  the  same  manner. 

Analyses.  Subs.,  0.3040,  0.2017,  0.3813:  cc.  0.1  N  KMnO4,  10.79,  7.09,  13.60. 
Calc.  for  C28H1808Ca.2H20:  Ca,  7.18.  Found:  7.11,7.04,7.15. 

Zinc  Salt. — (a)  This  salt  was  first  obtained  in  an  attempt  to  reduce  ^-hydroxy- 
benzoyl-o-benzoic  acid  in  aqueous  solution  with  zinc  dust.  A  solution  of  10  g.  of  the  acid 
in  750  cc.  of  water  was  boiled  with  1  g.  of  zinc  dust  for  15  hours,  and  then  filtered  to  re- 
move the  excess  zinc.  On  standing,  clusters  of  colorless  crystals  separated.  The  salt, 
purified  by  recrystallization  from  hot  water,  melts  at  80-81  °.  It  is  very  soluble  in  hot 
95%  alcohol  and  difficultly  soluble  in  hot  water.  It  melts  under  boiling  water.  When 
hydrolyzed  by  acids  it  gives  £-hydroxybenzoyl-0-benzoic  acid.  Some  of  the  air-dried 
material  was  analyzed. 

Analyses.  Subs.,  0.2008,  0.2019,  0.3017:  ZnNH4PO4,  0.0531,  0.0532,  0.0799; 
Zn2P2O7,  0.0447,  0.0449,  0.0672.  Calc.  for  C28H18O8Zn.7H2O :  Zn,  9.70;  calc.  for 
C28H18O8Zn.7.5  H2O:  Zn,  9.58;  calc.  for  C28Hi8O8Zn.8H2O :  Zn,  9.45.  Found:  Zn  calc. 
from  ZnNH4PO4:  9.69,  9.66,  9.71;  Zn  calc.  from  Zn2P2O7:  9.55,  9.54,  9.55. 

In  order  to  determine  whether  the  salt  crystallizes  with  7,  7.5,  or  8  molecules  of  water, 
samples  were  heated  to  constant  weight  in  a  drying  tube  at  81  °.  Water  was  seen  to 
condense  on  the  sides  of  the  tube  and  the  salt  turned  yellow. 

Analyses.  Subs.,  0.2538,  0.2430:  loss  at  81°,  0.0503,  0.0486.  Calc.  for  C28H18O8- 
Zn.7H20:  H2O,  18.72;  calc.  for  C2sH18O8Zn.7.5H2O:  H2O,  19.78;  calc.  for  C28H18O8Zn.- 
8H20:  H20,  20.83.  Found:  19.81,  20.00. 

These  results  indicate  that  the  zinc  salt  crystallizes  with  7.5  molecules  of  water. 
The  anhydrous  salt  was  also  analyzed. 

Analyses.  Subs.,  0.2035,  0.1944:  ZnNH4PO4,  0.0660,  0.0641;  Zn2P2O7,  0.0556, 
0.0534.  Calc.  for  C28H18O8Zn:  Zn,  11.94.  Found:  Zn  calc.  from  ZnNH4PO4,  11.88, 
12.14;  Zn  calc.  from  Zn2P2O7,  11.72,  11.78. 

(b).  The  same  salt  was  prepared  by  heating  an  aqueous  solution  of  />-hydroxy- 
benzoyl-o-benzoic  acid  with  zinc  carbonate.  It  crystallizes  in  clusters  of  colorless  plates 
melting  at  80-81  °.  Analyses  of  the  air-dried  material  gave  results  which  agreed  with 
those  obtained  for  the  preceding  zinc  salt. 


1522  W.  R.  ORNDORFF  AND  LOUISE 

Analyses      Subs.,  0.3021,  0.3042,  0.2511:     ZnNH4PO4,  0.0799,   0.0798,    0.0661; 
Zn2P207,  0.0669,  0.0668,  0.0556.      Calc.  for  C28H18O8Zn.7.5H2O :    Zn,  9.58. 
Zn  calc.  from  ZnNH4PO4,  9.69,  9.61,  9.64;  Zn  calc.  from  Zn2P2O7,  9.49,  9.42,  9.49. 

Diacetate.— (a)  One  part  of  £-hydroxybenzoyl-o-benzoic  acid  was  boiled  with 
6  parts  of  acetic  anhydride  for  2  hours  and  the  solution  was  then  poured  into  cold  water. 
A  colorless  oil  separated,  which  solidified  after  a  time  giving  white  crystals  which  were 
removed  from  the  liquor  by  filtration  and  dried.  This  material  melted  at  137-140° 
Miss  Murray10  states  that  a  sharper  melting  point  could  not  be  obtained,  but  it  was  found 
that  recrystallization  from  acetic  acid  and  then  from  95%  alcohol  gave  a  very  pure  prod- 
uct melting  at  162-163  °.  The  diacetate  is  converted  by  treatment  with  warm  alcoholic 
sodium  hydroxide  or  cone,  sulfuric  acid  into  £-hydroxybenzoyl-0-benzoic  acid. 

The  desiccator-dried  material  was  analyzed  by  determining  the  number  of  acetyl 
groups,  using  a  modification  of  the  Wenzel  method.11 

Analyses.  Subs.,  0.2009,  0.2011:  cc.  O.I  N  iodine,  0.00,  0.00;  cc.  net  0.1  N  NaOH, 
12.34,  12.36.  Calc.  for  Ci4H8O4(C2H3O)2:  C2H3O,  26.38.  Found:  26.43,  26.45. 

(b).  One  part  of  £-hydroxybenzoyl-o-benzoic  acid  was  boiled  with  one  part  of 
fused  sodium  acetate  and  8  parts  of  acetic  anhydride  foj  2  hours.  The  diacetate  so 
obtained  melted  after  recrystallization  from  hot  95%  alcohol  at  162-163°.  Analysis  of 
the  pure,  dried  material  gave  the  following  results.  ~;  ,'  " 

Analyses.  Subs.,  0.2004,  0.2001 :  cc.  0.1  N  iodine,  0.10,  0.00;  cc.  net  0.1  N  NaOH, 
12.28,12.24.  Calc.  for  Ci4H804(C2H30)2:  C2H3O,  26.38.  Found:  26.37,26.32. 

The  structure  of  the  diacetate  of  £-hydroxybenzoyl-o-benzoic  acid  is  as  follows. 
CH3COOC6H4C(OCOCH3)C6H4 

O C=0 

Ethyl  Ester. — Fifteen  g.  of  £-hydroxy-benzoyl-0-benzoic  acid  was  dissolved 
in  75  cc.  of  95%  alcohol  and  to  the  solution  was  added  15  cc.  of  cone,  sulfuric 
acid.  The  solution  was  boiled  for  3  hours  and  was  then  poured  into  dil.  sodium  car- 
bonate solution  containing  enough  sodium  carbonate  to  neutralize  the  sulfuric  acid 
present.  A  colorless  oil  separated  which  solidified  on  standing  for  several  hours.  The 
reaction  is  as  follows: 

HOC6H4C(OH)C6H4  +  C2H5OH  — >  HOC6H4C(OH)2C6H4COOC2H5  — > 

HOC6H4COC6H4COOC2H5  +  H2O 
O C=O 

The  ester  was  recrystallized  several  times  from  large  amounts  of  hot  water  in  which 
it  is  not  very  soluble.  On  cooling,  the  solutions  become  milky  in  appearance  and  then 
deposit  colorless,  needle-like  crystals,  which  melt  at  114-115°.  The  ester  is  very  soluble 
in  hot  95%  alcohol,  cold  methyl  alcohol  and  hot  acetic  acid.  When  dissolved  in  5% 
sodium  hydroxide  it  is  converted  into  £-hydroxybenzoyl-o-benzoic  acid.  A  desiccator- 
dried  sample  was  analyzed. 

Analyses.  Subs.,  0.1802,  0.1822:  CO2,  0.4700,  0.4753;  H2O,  0.0864,  0.0857.  Calc. 
forCi6H14O4:  C,  71.09;  H,  5.22.  Found:  C,  71.15,  71.17;  H,  5.37,  5.26. 

ACTION  OF  DRY  AMMONIA  GAS  ON  THE  ETHYI..ESTER.— When  dry  ammonia  gas  was 
passed  over  the  dry  ethyl  ester,  the  ester  absorbed  ammonia  and  turned  a  lemon-yellow 
very  rapidly.  It  finally  formed  a  gummy,  greenish-yellow  mass.  At  this  point  it  had 
absorbed  ammonia  to  constant  weight  and  the  values  obtained  corresponded  with  those 
calculated  for  one  molecule  of  ammonia. 


10  Murray,  THIS  JOURNAL,  39,  680  (1917). 

11  Wenzel,  Monatsh.,  18,  659  (1897).     Compare  Orndorff  and  Brewer,  Am.  Chem 
J.,  26,  121  (1901)  and  Orndorff  and  Delbridge,  ibid.,  42,  227  (1909). 


DERIVATIVES  OF  HYDROXYBENZOYIv-BENZOIC  ACID  1523 

Analyses.  Subs.,  0.3279,  0.1764:  wt.  of  salt,  0.3486,  0.1875.  Calc.  for  Ci6H14O4. 
(NH3):  NH3,  5.93.  Found:  5.94,5.92. 

One  of  the  samples  was  placed  in  an  evacuated  desiccator  over  cone,  sulfuric  acid 
for  several  days.  It  lost  slightly  less  than  :/2  of  the  ammonia  which  it  had  absorbed. 

Analysis.  Subs.,  0.3279:  wt.  of  salt,  0.3389;  NH3  remaining,  0.0110.  Calc.  for 
C16H1404.(NH3)o.5:  NH3,  3.05.  Found:  3.25. 

After  standing  in  the  desiccator  for  several  more  days  there  was  no  further  decrease 
in  weight,  so  the  amount  of  ammonia  present  was  determined  by  titration.  After  re- 
moval of  the  ammonia,  the  ethyl  ester  crystallized. 

Analysis.  Subs.,  0.3389:  cc.  0.1  N  HC1,  6.46;  NH3  remaining,  0.0110  g., 
3.25%.  Found  by  titration:  0.0110  g.,  3.25%.  . 

In  order  to  make  sure  that  the  increase  in  weight  was  due  to  the  absorption  of 
ammonia  and  that  no  other  action  had  occurred,  the  ammonia  in  the  second  sample  was 
determined  by  titration. 

Analysis.  Subs.,  0.1875:  cc.  0.1  N  HC1,  6.53;  wt.  of  ammonia  absorbed,  0.0111; 
found  by  titration,  0.0111.  Calc.  for  CieHuO^ (NH3) :  NH3,  5n93.  Found  by  titration : 
5.93. 

The  reaction  of  the  ethyl  ester  with  ammonia  is  as  follows:  HOCeUjCOCeHU- 
COOC2H6  +  NH3  — >  NH4OC6H4COC6H4COOC2H6. 

The  compound  is  not  stable,  as  it  loses  a  portion  of  the  ammonia  when  left  in  an 
evacuated  desiccator  over  cone,  sulfuric  acid. 

Methyl  Ester. — This  ester  was  prepared  from  the  acid  and  methyl  alcohol.  It 
is  very  soluble  in  hot  95%  alcohol  and  hot  glacial  acetic  acid.  It  is  recrystallized  from 
hot  water  in  which  it  is  readily  soluble.  It  crystallizes  in  needles  melting  at  149-150°. 
A  sample  of  the  desiccator-dried  ester  was  analyzed. 

Analyses.  Subs.,  0.1802,  0.1883:  CO2,  0.4623,  0.4841;  H2O,  0.0770,  0.0816.  Calc. 
for  Ci5H1204:  C,  70.29;  H,  4.72.  Found:  C,  69.99,  70.14;  H,  4.78,  4.85. 

Professor  Gill  states  concerning  this  ester:  "The  crystals  are  certainly  triclinic  and 
the  occurrence  of  frequent  truncation  of  one  sharp  end  without  a  corresponding  face 
at  the  other  end  seems  to  indicate  the  rather  rare  pedial  symmetry.  The  double  re- 
fraction is  very  strong, — not  less  than  0.200." 

ACTION  OF  DRY  AMMONIA  GAS  ON  THE  METHYI,  ESTER. — When  dry  ammonia  gas  was 
passed  over  the  methyl  ester  of  £-hydroxybenzoyl-o-benzoic  acid,  the  ester  turned 
greenish-yellow  and  seemed  to  become  semi-liquid.  When  the  material  had  come  to 
constant  weight,  the  increase  in  weight  showed  that  the  substance  had  absorbed  more 
thanl,  but  less  than  1.5,  molecules  of  ammonia  to  1  molecule  of  the  ester. 

Analyses.    Subs.,  0.1463,  0.1258:   wt.  of  salt,  0.0588,  0.1364.     Calc.  for  Ci5Hi2O4.- 
(NH3):   NH3,  6.23;  calc.  for  C^H^-CNHgVe:   NH3,  9.06.     Found:   7.87,7.77. 
The  ammonia  absorbed  by  Sample  II  was  determined  by  titration. 
Analysis.     Subs.,  0.1364:  cc.  0.1  NHC1,  6.35.     NH3  absorbed:  0.0106  g.     Found 
by  titration:    0.0108  g.,  7.92%. 

3,5-Dibromo-4-hydroxybenzoyl-0-benzoic  Acid. — Tetrabromo-phenolphthalein-ox- 
ime  was  prepared  by  Friedlander  and  Stange12  by  the  action  of  hydroxylamine  hydro- 
chloride  on  an  alkaline  solution  of  tetrabromo-phenolphthalein.  This  oxime  is  de- 
composed by  boiling  with  dil.  sulfuric  acid  into  dibromo-/>-hydroxybenzoyl-0-benzoic 
acid  and  dib.romo-amidophenol.  The  acid,  recrystallized  from  glacial  acetic  acid,  melts 
at  246-248°. 

i2  Friedlander  and  Stange,  Ber.,  26,  2260  (1893). 


1524  W.  R.  ORNDORFF  AND  LOUISE 

This  acid  was  made  in  the  following  way.  One  part,  by  weight,  of  p-hydroxyben- 
zoyl-0rbenzoic  acid  was  dissolved  in  6  parts  of  hot  glacial  acetic  acid,  and  to  the  cooled 
solution  5%  in  excess  of  2  molecules  of  bromine  to  1  of  the  hydroxy  acid  was  added,  and 
the  mixture  allowed  to  stand  overnight.  The  colorless  crystals  obtained  were  filtered 
off,  washed  with  glacial  acetic  acid  and  dried  in  the  air.  The  compound  is  easily  soluble 
in  hot  95%  alcohol,  hot  methyl  alcohol  and  hot  glacial  acetic  acid.  Recrystallized  from 
glacial  acetic  acid,  it  melts  sharply  at  250°. 

The  dibromo  compound  was  analyzed  by  Mr.  H.  A.  Bedient  in  this  laboratory. 
Analysis  I  was  made  by  the  lime  method,13  while  Analysis  II  was  carried  out  by  fusion 
of  the  sample  with  2  g.  of  powdered  potassium  nitrate  and  8  g.  of  ground  potassium 
hydroxide  (halogen-free)  in  a  nickel  crucible  and  analysis  of  the  product  as  in  the  lime 
method. 

Analyses.  Subs.,  (I),  0.2000,  (II)  0.1688:  cc.  0.1  N  AgNO3,  (I)  9.93,  (II)  8.50. 
Calc.  for  Ci4H8O4Br2:  Br,  39.96.  Found:  (I)  39.68,  (II)  40.24. 

£-Hydroxybenzoyl-0-benzoic  Acid  Phenylhydrazone. — Kaiser14  has  prepared  the 
phenylhydrazone  of  diphenyl-phthaloylic  acid,  and  0-benzoylbenzoic  acid  phenylhydra- 
zone  has  been  made  by  Roser15  and  also  by  H.  Meyer  and  Turnau.16 

Ten  g.  of  finely  powdered  />-hydroxybenzoyl-0-benzoic  acid  was  heated  with  9  g. 
of  phenylhydrazine  (calculated  4.2  g.)  at  160°.  Water  vapor  was  evolved  and  the  mate- 
rial turned  yellow.  After  3  hours  the  heating  was  discontinued  and  the  material  in  the 
flask  was  treated  with  water  containing  some  hydrochloric  acid.  The  crystalline  product 
was  filtered  off,  dried  and  recrystallized  from  hot  95%  alcohol.  The  phenylhydrazone 
crystallizes  as  small,  colorless  needles  melting  at  267-268°.  It  is  soluble  in  hot  glacial 
acetic  acid. 

Analyses.  Subs.,  0.1795,  0.1819:  CO2,  0.5037,  0.5100;  H2O,  0.0726,  0.0784. 
Calc.  for  C2oH1402N2:  C,  76.41;  H,  4.49.  Found:  C,  76.55,  76.49;  H,  4.53,  4.82.  Subs., 
0.1566:  cc.  0.1  AT  H2SO4,  9.62.  Calc.  for  C20H14O2N2:  N,  8.91.  Found:  8.60. 

The  formula  of  the  phenylhydrazone  may  be  written: 
HOC6H4C C6H4 

II  '  I 

N— N(C6H6)— C=O 

Hydroxy-phenylphthalide. — Hydroxy-phenylphthalide  was  prepared  by  Bis- 
trzycki  and  Oehlert17  by  condensing  phthalaldehydic  acid  with  phenol.  Their  product 
melted  after  previous  softening  at  148-151°,  and  its  acetate  melted  at  125-126.5°. 
Hans  Meyer18  obtained  hydroxy-phenylphthalide  by  reducing  />-hydroxybenzoyl-0- 
benzoic  acid  in  alcoholic  solution  with  zinc  and  hydrochloric  acid.  His  product  melted 
at  157-160°,  and  the  acetate  melted  at  125-126°. 

Ten  g.  of  ^-hydroxybenzoyl-o-benzoic  acid  was  dissolved  in  75  cc.  of  95%  alcohol 
and  to  this  solution  was  added  3  g.  of  zinc  and  8  cc.  of  cone,  hydrochloric  acid.  The 
solution  was  boiled  for  2V2  hours  and  then  filtered  while  hot  into  4  liters  of  hot  water. 
A  yellow  oil  separated  and  later  solidified.  It  was  recrystallized  by  dissolving  it  in  as 
small  an  amount  of  hot  95%  alcohol  as  possible  and  pouring  the  hot  solution  into  hot 
water.  Hydroxy-phenylphthalide  crystallizes  as  small,  colorless  needles  melting  at 
164-165°.  It  is  very  soluble  in  hot  95%  alcohol  and  in  hot  glacial  acetic  acid.  A 
desiccator-dried  sample  was  analyzed. 

13  Am.  Chem.  J.,  41,  397  (1909). 

14  Kaiser,  Ann.,  257,  98  (1890). 

15  Roser,  Ber.,  18,  805  (1885). 

16  Meyer  and  Turnau,  Monatsh.,  30,  483  (1909). 

17  Bistrzycki  and  Oehlert,  Ber.,  27,  2632  (1894). 

18  Meyer,  Monatsh.,  20,  363  (1899). 


DERIVATIVES  OF  HYDROXYBENZOYL-BENZOIC  ACID  1525 

Analyses.  Subs.,  0.1814,  0.1800:  CO2,  0.4952,  0.4898;  H2O,  0.0767,  0.0745.  Calc. 
forCuH10O3:  C,  74.32;  H,  4.46.  Found:  C,  74.47,  74.23;  H,  4.73,  4.63. 

ACETATE. — The  acetate,  prepared  by  heating  one  part  of  hydroxy-phenylphthalide 
with  one  part  of  fused  sodium  acetate  and  20  parts  of  acetic  anhydride,  was  recrystallized 
from  hot  95%  alcohol,  in  which  it  is  very  soluble.  It  crystallizes  as  small,  colorless 
needles,  melting  with  previous  softening  at  125-126°.  A  desiccator-dried  sample  was 
analyzed. 

Analyses.  Subs.,  0.1831,  0.1850:  CO2,  0.4813,  0.4845;  H2O,  0.0748,  0.0748. 
Calc.  for  C16H12O4:  C,  71.62;  H,  4.51.  Found:  C,  71.71,  71.45;  H,  4.57,  4.52. 

Professor  Gill  states  concerning  this  acetate:  "The  double  refraction  in  the  plates 
is  about  0.050,  making  the  maximum  for  the  substance  about  0.100.  The  crystals  are 
without  much  doubt  triclinic,  simulating  rhombic  shape." 

Hydroxy-phenylphthalide  may  be  represented  by  Formula  I  and  the  acetate  by 
Formula  II. 

HOC6H4CH— C6H4  CH3COOC6H4CH— C6H4 

II  II 

o — c=o  o — c=o 

I  II 

£-Methoxybenzoyl-0-benzoic  Acid. — £-Methoxybenzoyl-o-benzoic  acid  was  first 
prepared  in  1886  by  Nourrisson19  by  condensing  phthalic  anhydride  with  anisol  in  the 
presence  of  aluminum  chloride.  The  acid  melted  at  142-143  °.  Nourrisson  gave  it  the 
ketone  structure.  In  1909  Hans  Meyer  and  Turnau20  prepared  this  acid  by  shaking  a 
solution  of  £-hydroxybenzoyl-0-benzoic  acid  in  sodium  carbonate  or  sodium  hydroxide 
solution  with  a  slight  excess  of  dimethyl  sulfate.  The  acid,  recrystallized  from  alcohol, 
melted  at  148°. 

£-Methoxybenzoyl-0-benzoic  acid  was  prepared  in  this  laboratory  by  Mr.  Frederick 
Nill.  He  made  it  from  phthalic  anhydride  and  anisol,  using  a  modification  of  the  earlier 
methods.  The  materials  were  kept  in  a  closed  flask  surrounded  by  an  ice-bath,  the 
temperature  of  which  was  — 5°  to  — 10°,  and  the  aluminum  chloride  was  added  in  small 
portions.  The  flask  was  evacuated  after  each  addition  of  aluminum  chloride.  Finally, 
the  temperature  was  slowly  raised  to  55°,  hydrochloric  acid  was  added,  and  the  excess 
of  anisol  present  removed  by  distillation  with  steam.  The  acid,  which  crystallized 
from  the  solution  remaining  in  the  flask,  melted  at  141.5-142°. 

Ten  g.  of  £-hydroxybenzoyl-o-benzoic  acid  was  dissolved  in  100  cc.  of  5%  sodium 
hydroxide  and  to  the  solution  was  added  5  g.  of  dimethyl  sulfate.  The  mixture  was 
boiled  for  2:/2  hours  and  then  diluted  to  2  liters.  Addition  of  acetic  acid21  to  the  alkaline 
solution  resulted  in  the  formation  of  an  oil  which  later  solidified.  The  acid  is  easily 
recrystallized  from  water  from  which  it  separates  on  cooling,  first  as  an  oil  and  then  as 
thin,  colorless  plates.  After  several  recrystallizations  it  melts  at  144-145°.  The  acid 
crystallizes  well  from  hot  alcohol  and  Jiot  glacial  acetic  acid.  Hydrochloric  acid  con- 
verts it  into  the  hydroxy  acid.  A  desiccator-dried  sample  was  analyzed. 

Analyses.  Subs.,  0.1921,  0.2007:  CO2,  0.4960,  0.5166;  H2O,  0.0858,  0.0850. 
Calc.  for  C16H12O4:  C,  70.29;  H,  4.72.  Found:  C,  70.44,  70.22;  H,  4.99,  4.74. 


19  Nourrisson,  Ber.,  19,  2103  (1886). 

20Ref.  17,  p.  485. 

21  Nill,  in  precipitating  £-methoxybenzoyl-0-benzoic  acid  from  alkaline  solution 
by  means  of  hydrochloric  acid,  found  that  when  an  excess  of  the  mineral  acid  was  used, 
a  substance  melting  at  186-187  °  was  obtained.  This  substance  was  doubtless  a  mixture 
of  the  methoxy  and  hydroxy  acids. 


1526  W.  R.  ORNDORFF  AND  LOUISE 

p-Methoxybenzoyl-0-benzoic  acid  titrates  as  a  monobasic  acid.  Methyl  red  was 
used  as  indicator. 

Analyses.  Subs.,  0.3001,  0.2997,  0.5000:  cc.  0.1  N  NaOH,  11.72,  11.69,  19.51. 
Calc.  for  Ci5H1204:  256.17.  Found:  256.06,  256.37,  256.27. 

£-Methoxybenzoyl-o-benzoic  acid  probably  has  the  lactone  structure  in  the  free 
state  and  the  ketone  structure  in  its  salts. 

ACTION  OP  DRY  AMMONIA  GAS. — Dry  ammonia  gas  was  passed  over  some  of  the 
dried  acid  for  6  hours,  when  the  latter  came  to  constant  weight.  The  material  acquired 
a  faint  yellow  tinge.  The  gain  in  weight  corresponded  to  the  addition  of  1.5  molecules 
of  ammonia  to  one  of  the  acid.  f 

Analyses.  Subs.,  0.4133,  0.5574:  wt.  of  salt,  0.4544,  0.6125.  Calc.  for  Ci6H12O4.- 
(NH3)i.6:  NH8,  9.06.  Found:  9.04,  9.00. 

After  standing  in' an  evacuated  desiccator  over  cone,  sulfuric  acid  for  a  few  days  the 
material  came  to  constant  weight  when  1  molecule  of  ammonia  remained. 

Analyses.  Subs.,  0.4133,  0.5574:  wt.  of  salt,  0.4406,  0.5944.  Calc.  for  Ci6H12O4.- 
(NH3):  NH3,  6.23.  Found:  6.19,6.22. 

Unlike  the  ammonium  salt  of  the  hydroxy  acid,  this  salt  loses  weight  when  heated 
at  65  °  in  a  tube  in  a  current  of  dry  air  for  3  hours.  The  mono-ammonium  salt  is  color- 
ess.  It  is  very  soluble  hi  hot  water,  and  easily  soluble  in  cold  water  and  in  hot  95% 
alcohol. 

MONOSODIUM  SALT. — This  salt,  obtained  by  the  action  of  sodium  upon  />-methoxy- 
benzoyl-0-benzoic  acid  in  alcoholic  solution,  crystallizes  in  small,  colorless  needles, 
soluble  in  hot  95%  alcohol  and  very  soluble  in  hot  water.  The  desiccator-dried  salt  was 
analyzed. 

Analyses.  Subs.,  0.4062,  0.3606:  Na2SO4,  0.1039,  0.0916.  Calc.  for  Ci6HnO4Na: 
Na,  8.27.  Found:  8.28,  8.21. 

POTASSIUM  SALT. — This  salt  was  made  by  the  action  of  potassium  on  />-methoxy- 
benzoyl-o-benzoic  acid  in  alcoholic  solution.  It  crystallizes  in  clusters  of  long,  colorless 
needles,  very  soluble  in  cold  water  and  in  hot  95 %  alcohol.  It  melts  at  257  °  to  a  redctah 
oil.  Dried  hi  a  desiccator,  the  air-dried  salt  lost  only  about  2%  in  weight.  The  desic- 
cator-dried salt  was  analyzed  for  potassium. 

Analyses.  Subs.,  0.3018:  K2SO4,  0.0837.  Calc.  for  C15HnO4K.H2O :  K,  12.52; 
calc.  for  Ci6HnO4K.0.5C2H6OH:  K,  12.32.  Found:  12.45. 

Since  this  analysis  did  not  indicate  whether  the  salt  crystallizes  with  1  molecule  of 
water  or  with  1/2  a  molecule  of  alcohol,  and  since  when  dried  in  a  tube  at  125  °  the  salt 
did  not  lose  any  solvent  of  crystallization,  two  combustions  of  the  desiccator-dried  salt 
were  made. 

Analyses.  Subs.,  0.1809,  0.1747:  total  C,  0.1095,  0.1055;  H2O,  0.0640,  0.0623. 
Calc.  for  Ci6HuO4K.H2O:  C,  57.66;  H,  4.20;  calc.  for  CiaHnC^K.O.SCzHsOH : 
C,  60.54;  H,  4.45.  Found:  C,  60.53,  60.38;  H,  3.96,  3.99. 

METHYL  KsTER. — Hans  Meyer  and  Turnau21  found  that  £-methoxybenzoyl-0- 
benzoic  acid  gave  2  isomeric  methyl  esters.  One  ester,  melting  at  63  °,  was  prepared  by 
treating  £-hydroxybenzoyl-0-benzoic  acid  in  alkaline  solution  with  dimethyl  sulfate; 
the  other  ester,  melting  at  84  °,  was  obtained  by  treating  the  hydroxy  acid  with  thionyl 
chloride  and  then  with  methyl  alcohol.  They  gave  to  the  latter  ester  the  following 
structure. 

CH3OC6H4C(OCH3)— C6H4 

O C=0 

Ten  g.  of  £-hydroxybenzoyl-o-benzoic  acid  was  dissolved  in  100  cc.  of  10%  sodium 


DERIVATIVES  OF  HYDROXYBENZOYL-BENZOIC  ACID  1527 

hydroxide  solution  and  to  this  solution  contained  in  a  glass-stoppered  bottle  was  added 
an  excess  over  the  calculated  amount  of  dimethyl  sulfate.  The  solution  was  shaken  well. 
More  alkali  and  dimethyl  sulfate  were  added  alternately  from  time  to  time  and  the 
contents  of  the  bottle  were  shaken  well  after  each  addition.  A  colorless  oil  separated  and 
later  solidified.  The  ester  is  easily  recrystallized  from  hot  methyl  alcohol,  in  which  it 
is  very  soluble.  It  separates  in  colorless  crystals  melting  at  80-81.5°.  This  indicates 
that  it  is  identical  with  the  second  ester  mentioned  by  Meyer  and  Turnau.  Some  of  the 
desiccator-dried  ester  was  analyzed. 

Analyses.    Subs.,   0.1795,   0.1778:     CO2,   0.4678,   0.4636;   H2O,   0.0844,   0.0827. 
Calc.  for  Ci6H14O4:  C,  71.09;  H,  5.22.    Found:  C,  71.09,  71.13;  H,  5.26,  5.25. 

"Summary 

I1.     The  sodium,  silver,  barium,  calcium  and  zinc  salts  of  ^-hydroxy- 
benzoyl-o-benzoic  acid  have  been  prepared. 

2.  The  ethyl  and  methyl  esters  of  ^-hydroxybenzoyl-o-benzoic  acid 
have  been  prepared  and  the  action  of  ammonia  on  them  has  been  observed. 

3.  The  dibromo  derivative  of  £-hydroxybenzoyl-0-benzoic  acid  has  been 
prepared  by  direct  bromination  of  the  acid. 

4..    The  phenylhydrazone  of  £-hydroxybenzoyl-0-benzoic  acid  has  been 
prepared. 

5.  Hydroxy-phenylphthalide  and  its  acetate  have  been  prepared. 

6.  £-Methoxybenzoyl-0-benzoic  acid  and  its  sodium  and  potassium 
salts  and  methyl  ester  have  been  prepared. 

ITHACA,  NEW  YORK 


0X0%° T°  E 


507S- 


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